Tap chi Hoa hgc,
T. 48(6), Tr. 704 - 708, 2010
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TONG HOP VA CAU TAO CUA MOT SO DAN XUAT XET0N-a,;ff.KH6NG NO CHLfA NHAN D\ VONG
FURAN, PIROL, THIOPHEN VA PIRIDIN
Den Toa sogn 13-10-2008 NGUYEN DINH TRIEU', VU V A N H A '
'Khoa Hod hgc, Trudng Dgi hgc Khoa hgc Tu nhien, Dgi hgc Quo'c gia Hd Ngi 'Vien Hod hgc Cdng nghiep Viet Nam
ABSTRACT
Some derivatives of 2-fujyl-, 2-thienyl-, 2-N-methylpyrrolyl-, 2- and 3-pyridyl-aiylvinyl ketones have been synthesized by the condensed reaction of methylketones with the heterocyclic aldehydes. Their structure was identified by IR, 'H- and '^C spectra. The chargedensities on the carbon atoms of the main molecular skelete of 1-phenyl-, 1-(p-bromphenyl)- and l-(p- methylphenyl)-3-(2'-thieny!)-pro-2-en-l-one have been computed using chemical quantum AMI.
Cdc hgp chat xeton-a,y^khdng no da dugc nghien ciM nhilu vl phuang phdp tdng hgp cung nhu nhQng Qng dyng cua chung, dac biet la day 1,3-diphenyl t h i pro-2-en-l-on cd ten ggi la chalcone [1, 4, 5]. Trong cdng trinh nay chung tdi thdng bao kit qua tdng hgp va khao sat cau tnic cua mgt sd xeton- a,/?-kh6ng no chQa nhan
di vdng furan, thiophen, pirol, piridin.
D l tdng hgfp xeton-a.y^-khdng no cd nhieu phuang phap vdi nhilu loai xuc tac khac nhau, chung tdi chgn phugng phap ngung ty andol giua mgt andehit thom chQa di vdng va mgt arylmetylxeton.
A r — C H ^ O + C H 3 — C
Ar= 2-furyl, 2-thienyl, 2-N-metylpirolyl, 2-piridyl, 3-piridyl Y= H, CH3, Br.
Xuc tac cho phan ting ngung ty cd thi la axit, bazg vd ca nhu NaOH, KOH, bazo hQu ca nhu piperidin... cung nhilu loai dung mdi khac nhau. Do hgp phdn andehit cd chQa cac di vdng furan, pirol, thiophen la cac hgp phdn d l bi phd huy bdi nhiet vd keo hda bdi axit nen chung tdi chgn dung mdi etanol va xuc tac NaOH d nhiet do lanh. Day la dilu kien phu hgp cho hieu suat
cao va khdng bi phd buy cau tnic cua di vdng.
Cac xeton-«,y?-khdng no tdng hgp dugc diu cd dang tinh thi, cd mdu tu vdng nhat tdi vang dam, cd diem chdy xac dinh. San phdm dugc kit tinh lai trong etanol 80" de dat dugc do tmh khilt (bang 1). Cau tnic cua san pham dugc xac dinh bdng phuang phap phd IR, 'H-NMR, ''C-NMR [3].
Bdng 1: Mdt sd tfnh chdt cua xeton-a,>9-khdng no
Chdt 1 2 3 4 5 6 7 8 9
Ar 2-furyl 2-furyl 2-furyl 2-thienyl 2-thienyl 2-thienyl 2-N-metyl- pirolyl 2-piridyl 3-piridyl
Y H CH3
Br H CH3
Br Br Br Br
CTPT C13H10O2 C,4H,202 C]3H9Br02
C,3H,oSO C14H10SO C,3H9BrSO CnHijBrNO Ci4HioBrO C]4HioBrO
KEPT 198 212 277 214 228 293 290 288 288
T°nc, °C 47-48 71-72 83-84 61-62 134-135 107-108
115 126
Mdu Vdng nhat Vdng nhat Vdng nhat Vdng nhat Vang nhat Vang nhat Vang dam
Trdng Trdng
Hieu sudt, %
72 70 75 72 73 80 68 65 68 Phd hdng ngoai chi ra hdp thy dac trung cua nhdm C=0 d 1640 - 1685 cm"' vd C=C cua anken d 1549 - 1580 cm"', tdn sd hdp thy cua hai nhdm nay chuyen dich vl phfa tdn so thdp do cd su lien hgp cua chung. Gid tri 5(=CH) ndm d vung 995 - 960 cm' chi ra can tao trans ciia chung (bang 2).
Bdng 2: Phd hdng ngoai cua xeton-«,y0-khdng no
Chai 1 2
3
4 5 6 7 8 9
X 2-furyl 2-furyl
2-furyl
2-thienyl 2-thienyl 2-thienyl 2-N-metyl-
pirolyl 2-piridyl 3-piridyl
Y H CH3
Br
H CH3
Br Br Br Br
Vc=0
166,89 1650,35
1655,63
1649,47 1657,03 1647,92 1646,40 1685,67 1682,60
VCH=
971,60 973,54
973,80
978,38 : 963,77
974,33 970,22 985,43 990,46
^Cthom the para
817,09 740,11
821,48 . 710,08
Vc-o-c 1332,17 1280,93 1227,00 1325,72 1281,73 1221,24 C-Br 740,11
C-Br 710,08
C-Br 734,47
C-Br 746,59
C-Br 718,64 Tren phd cdng hudng tQ proton cua cdc d vi tri 7,7 vd 8,0 ppm vdi hdng sd tuang tdc J = xeton-a,/?-khdng no diu xudt hien cap pfc ndm 15 Hz thi hien su cd mat cua ndi ddi trans-vinyl
trong xeton-a,/?-khdng no chQng minh sy hinh thanh san phdm bdi phan ung Claisen-Smith.
Ngoai ra tren phd cdn cho thay cac proton cua nhan tham ndm trong khoang dich chuyen tQ 7 - 8 ppm vdi hdng sd tuong tac Jo,,,,,, = 8,5.
Tren phd cdng hudng tQ ''C cua xeton-a./3- khdng no deu xudt hien tin hieu cdng hudng cd do dich chuyin hoa hgc la 187,7 ppm dac trimg
cho tfn hieu cua nguyen tu cacbon trong nhdm C=0. Pic d 120 ppm dac trung cho tfn hieu cdng hudng cua nguyen tu C trong nhdm vinylic ndi tryc tilp vdi nhdm C=0, ngodi ra tren phd cdn xuat hien cdc pic ndm trong vung 110 ppm den 150 ppm dac trung cho cac nguyen tu C ciia nhan tham. Cac dinh phd thu dugc hoan toan phu hgp vdi cdng thuc du kiln (bang 4).
Bdng 3: Phd cdng hudng tQ proton cua mdt sd xeton-a,y8-]didng no 6 5
9 10
7 4 3 1
CH=CH—CO
Chat TT proton
5 ppm so dinh Hdng so
J(Hz) Chat TT proton
8 ppm so dinh Hdng so J,
Hz Chat TT proton
5, ppm so dinh Hdng so J,
Hz
3 2 7,500
2
h,--
6 2 7,533
2
12-3 =
7 2 7,500
2
J2 3 =
X = 0 ; Y=Br 3
7,583 2
= 15,5
5 7,218
2 h.6 =
6 6,700
4 3,5
7 7,294
2 h-6- 1,5
9; 13 7,998
2
J g - i o -
10;12 7,763
2
= 8,5 X = S; Y = Br
3 7,959
2
= 15,5
3 7,722
2
= 15,0
5 7,803
2 h-6 —
5 7,070
2
Js-fi —
6 7,200
4 5,0
7 7,705
2 J7-f,= 3,5
9; 13 8,026
2
J 9 - 1 0 -
10;12 7,765
2
= 8,5 X = N-metyl; Y = Br
6 6,190
4 5,5
7 7,100
2 J7-5=4,0
9; 13 8,030
2
J Q - I O "
10;12 7,50
2
= 8,5 SQ dung phuang phap ban kinh nghiem
AMI tdi uu hod cdu hinh cua xeton-a,y5-kh6ng no thu dugc kit qua sau:
-1- RMS gradient: 0,1 kcal/mol.
-1 Vdng lap tdi da 500.
^ Cac xeton diu cd cdu dang bin la cdu true phdng, cau hinh trans.
Bdng 4: Phd cdng hudng tQ hat nhan '""C cua mdt sd xeton-a,/?-khdng no
, r \ 4
3 2 ,
~~-CH=CH—CO X
13 12 Chat
TTC 5 ppm TTC
5 ppm Chat TTC 5 ppm TTC
5 ppm
3 1 187,765 7
146,364 6
1 187,783 7
133,071
X = 0 ; Y = Br 2
118,359 8
136,462 3
130,866 9;13
130,273 4 151,017 10;12 131,842
5 113,166 11 127,099 X = S; Y = Br
2 119,971 8 137,193
3 136,441 9;13
130,356 4 139,566 10;12 131,799
5 127,116 11 128,717
6 117,376
6 130,736
Mat do dien tfch thu duac nhu sau:
-0,148 0,160 ^0,127
-0,436'- -0,435
0,145
-0,148 B r
0,119
0 , 0 8 3 ; : : = = ^ ^ ^ ^ -0,437
,039 0,149
THUC NGHIEM
Dilm chay cua chdt dugc do theo phuang phdp mao quan tren mdy do dilm chay Stuart (Anh).
Phd IR do tren may Nicolet Impact 400 FT- IR (USA) vung budc sdng 4000 - 400 cm"' ep vien KBr.
Phd 'H va '^C-NMR do tren mdy Avance 500 MHz cua hang Bracker (EU) vdi dung mdi
dimetylsunfoxit (DMSO-d6) chdt chuan TMS.
Cdc aryl metylxeton va andehit di vdng dugc dilu chi theo tai lieu [2].
Dieu che'xeton-a/3-khdng no
Hod tan 0,05 moi andehit tham va 0,05 moi aryl metyl xeton vao 30 ml etanol tuyet ddi.
Khua'y va lam lanh hdn hgp phan Qng bdng nudc dd de nhiet do xud'ng dudi 5°C, nhd 10 gigt dung die NaOH 25% vao hdn hgp phan Qng. Tmng
hgp phan ung,xudt hien cdc tinh the mau vdng.
Lgc va kit tmh lai bdng etanol 80°.
Kit qua cho d bang 1.
1.
2.
T A I LIEU THAM K H A O
Nguyin MQih Thdo, Pham Van Phong, Nguyin Thi Nhung, Nguyin Thi Sen, Dao Thi Thao. Tap chf hod hoc, T. 44(4) 44 (2006).
Phan Td'ng Son, Le Dang Doanh (dich).
Thyc hanh Hoa hgc huu eg, tap 1 (1976), 4.
5.
tap 2, Nxb. PChoa hgc va Ky thuat Ha Ndi (1977).
Nguyin Dinh Trieu. Cac phuang phdp phan tfch vat ly va hoa ly, tap 1, Nxb. Khoa hgc vdKy thuat. Ha Ngi (2001).
M. B. Austm, J. P. Noel. Natural Poroducts Reports, 20, 97 - 100 (2003).
I. M. Jez, J. P. Noel. Joumal of Biological Chemistty, 275, 39640 - 39646 (2000).
Ryuji Ueno, tomio Oda. U.S Patent 6,637,647 (1995).
Lien he: Vu Van Ha Khoa Hda hgc
Tmdng Dai hgc Khoa hgc Ty nhien Dai hgc Qud'c gia Ha Ngi
19 Le Thanh Tdng, Hoan Kilm, Ha Ngi Email: vuha chemist(a),vahoo.com.vn
